Polycarbonate (PC) wastes, including optical discs (CDs) and digital optical discs (DVDs), were chemically recycled into valuable materials such as 4,4′-(propane-2,2-diyl)diphenol (BPA) and etherified derivatives of BPA using sodium hydroxide (NaOH) as the alkali metal catalyst and nanostructured titanium dioxide (nano-TiO2) and microstructured titanium dioxide (micro-TiO2) as the solid supports in the binary green system consisting of water and 2,2′-oxydi(ethan-1-ol) (DEG) under conventional heating method, and data were compared. In this study, the effects of various parameters, such as solvent composition, concentration of NaOH, and solid support, were studied on the reaction progress. In these reactions, the importance of water as the green solvent was investigated in achieving pure BPA as the valuable material. When used with 20% aqueous DEG (pbw), a pure BPA can be obtained at 70% yield in the presence of nano-TiO2 and micro-TiO2 as the solid supports. According to the results, the use of nano-TiO2 in comparison with micro-TiO2 accelerates the chemical recycling of PC wastes. The nano-TiO2 catalyst recovery shows that the recovered solid support is applicable for four cycles. The obtained products were characterized using spectroscopic methods, namely, 1H NMR, 13C NMR, and Fourier transform infrared spectroscopy as well as gas chromatography-mass spectrometry.